Compound of sulfur dyes soluble in water.



. UNITED sTAtrEsfrnTENT OFFICE.

' mir. HAUSSMANN, or 'rnnr'row, NEAR-BERLIN, GERMANY, assrenoa 'ro Acrrian GEsELLs'cnArr FUR ANILIN rumination, or nnnnriv, GERMANY.

coriroum: or sunrun DYES SOLUBLE IN WATER.

953,008. li o Drawing.

vented certain new and useful Improvements in New Com ounds of Sulfur Dyes Soluble Water, 0 which the following is a specification.

My present invention relates to the manufacture of new compounds of sulfur dyestufl's soluble in water. These new compounds are obtained by the action of a suitable oxidizing agent on the aqueous solution of sulfur .dyestufis which are obtained b dissolving a sulfur dyestufi in water witi the addition of a sulfite of an alkali. On introducing a current of air into such an aqueous solution the sulfurd'yestufi's are not precipitated as was the'next to be expected, ecause the sulfite is converted into suifa'te,

but while the coloration of the solution is I strongly altered and darkened new coms. are formed which dye neither wool nor cotton. These substances may be isolated by evaporating the solution; and as they are very easil dissolved in water they may also be ofifere for commercial purposes in the form of a highly concentrated solution. This result is ver surprising because according to literature t e heretofore known sulfite-compounds of sulfur-dyestuffs, which are taken as leucocompounds (com are German patent 146,797) or as thiosul onic acids (compare English Letters Patent 15,413/00 and 16,414/00), are described as slightly colored compounds which according to German patents 88,392, 91,720'vand 94,501 directly dye cotton' and according to French patent 303,524 can be fixed on wool. My new compounds, which do not dye either cotton or wool are especially-fit for dyeing leather and most suitable for dyeing the so-called chrome-leather; for this purpose they are used in the .form of an a ueous solution with the addition of a smal 0- portion of a mineral acid, such assul uric acid, or of an organic acid, such as formic acid. When adding to an aqueous solution of these products a salt of a metal, such as copper, lead, barium, aluminium and the like, deeply can be use'd/ for dyeingpaper and. the like.

As oxidizing agents ifo'r the purpose of s -eomeatmn of Letters Patent. Application area February 4, 1909. Serial No. 476,182.

colored lakes are'obtaine'd which Patented Mar. 22, 1910'.

my present invention I find atmospheric air especially suitable, but other agents which will convert sodium sulfite into sodium sulfate, such as for example hydrogenperoxid,

sodium h pochlorite, ammonium-persulfate and the like, may aso be employed.

The following examples may serve to illustrate my invention, the parts being by weight: 7

1. 1000 artsof sulfur blue L'extra are ti'eetedwi h boiling water in order to 'elifninate the'inorg'anic soluble salts -and after filtering the. residue is dissolved in 9000 parts of boiling water with the addition of 1500 parts of crystallized sodium sulfite, a current of air bein blown through the mass at the same time. i he treatment of the boilin solution with air is'continued until the co oration of the solution does not change further. The solution is then filteredi t'o eliminate any smallquantities of insoluble products and the filtrate evaporated. The product thus obtained produces from an aqueous solution containing a small no ortion of an acid dark blue shades on eat er.

2. 1000 parts of sulfur black A extra in the form of moist press-cake, as it is obtained for instance by blowing a current of air through the mass of reaction anddraining is introduced While stirring into 1250 parts of boiling water; to this mass are added 1250 parts of crystallized sodium 'sulfite .whereupon boiling is continued until the dyestuflf has dissolved. The solution thus obtained, whiclris dirty een and on the addition of diluted suliuric acid is totally precipitated yielding a brown-gray precipitate, is-further treated with "air and then assumes a more bluish coloration whichdeepens. hen the change of the color ceases the radually increases toblue and mass is diluted withwater up" to 3000 arts. The solution thus obtained may be 0 end for commercial purposes. By evaporatin the solution as above obtained, the new pro appears as a black powder which easily dissolves in water to' a deep blue-blackcolored' v not is obtained which, -when pu1veriz'ed,'.

new product does not dye either avegetable or an animal fiber even if anv alkali or an acid or a usual neutral salt has been added f results which on the addition of hydrogen to the aqueous solution but with the: addition of suflicient acid dyes leather, and more "especially the so-called chrome-leather, black shades. This'new compound when dyed with the addition of an alkali sulfid has,

, compared with the original product, only a relativelyvery small a nity to the vegetable fiber. In aqueous solution it eliminates sulfurous acid on the addition of a mineral acid. If dissolved in water deeply colored lakes are obtained by the addition of a salt of .copper, lead, barium, aluminum and like metals, which lakes are suitable for examplefor coloring paper or like purposes. 1

3. 100 parts of immedial-black V extra are mixed with boiling water, and precipitated by adding a suitable proportion of diluted sulfuric acid. The resulting product is drained, washed with water and then introduced into an aqueous solution of 100 parts of neutral sodium sulfite in 1000 partsof water. After having boiled fol-about 5 hours the small quantity of undissolved dyestufi is separated by filtering, and a bottlegreen and rather slightly colored solution ,peroxid assumes immediately a deep blue color and which by the addition of an acid is not precipitated. Into the warm solution a current of air is introduced until the intensity of the color no longer increases and no further change of tint occurs. The solu- .t1on 1s then evaporated to dryness.

. scope of my invention; as examples of such other dyestuffs I may mention by way of example the difl'erent commercial marks of sulfur black, among others sulfur black T extra, 2 B extra, 4 B extra, or other black sulfur dyestuffs well known under the trade name ofimmedial black, katigen black, thiogenblack; thiophenol black, thion black, thioxin black and the like. Furthermore such blue or yellow or green sulfur dyestuffs which are soluble in sodium sulfite may be employed instead of the dyestuffs used in the foregoing examples.

It is obvious to those skilled in the art that when using such other dyestuffs in carrying outmy present invention thespecial conditions of reaction must be altered in order to obtain the best results with my new process, the characteristic feature of my process being the action; of a sulfite,v of an alkali and of an oxidizing agent, simultaneously or successively, on a sulfur dyestufl preferably in aconcentrated form, which concentrated form may be obtained 'elther by treating a commercial form of a sulfur dyestufl' insoluble in'water with preferably hot water in order to eliminate inorganic,

salts, or by separating the crude dyestuffs from the mass of reaction by diluting with Water'a'nd blowing a current ofiair through the solution, or acidifying thesolution.

For the sodium sulfite employed in the foregoing examples other normal alkall sulfites may be substituted.

Having now described the manner in which the same 'ried out whatl claim is,---- I 1. As new articles of manufacture, the new compounds of sulfur dyestuffs soluble in water which may be obtained by the action of an alkali sulfite in connection with maybe car'- my invention and an oxidizing agent adapted to convert sodium sulfite into sodium sulfate, for example atmospheric air, hydrogen peroxld and the like, upona sulfur dyestufl, these compounds when evaporated and pulverized being dark. to black colored owders, the aqueous solutions of which eliminate sulfurous acid on the addition. of a "mineral acid, and which in an aqueous solution on the addition of an aqueous solution of a salt (of copper, lead, barium, aluminum and like metals separate deeply colored lakes.

2., Asa new article of manufacture, the.

compound of sulfur dyestufi soluble inwater obtained by the action of an alkali sulfite in connection with atmospheric air upon a sulfur dyest-ufi' and evaporating and pulverizing the dry residue, this compound eing a dark toblack colored powder, the aqueous solution of which eliminates sulfurous acid on the addition vof a mineral acid, and which in an aqueous solution on the addition of an aqueous solutionrofa salt of copper, lead, barium, aluminum'and like metals separates deeply colored lakes.

3. As a new article of manufacture thenew compound soluble in water, which may be obtained by the action of an alkali sulfite in connection with atmospheric air- .upon sulfur black A extra, evaporating and pulverizing the dry residue, this new compound being a. black powder, which easily dissolves in water to a deep "blue colored solution,

which solution in a rather dilute form shows a greenish blue tint and is not precipitated by the addition of a dilute sulfuric acid, but' turns tored blue, which new compound doesnot dye either a' vegetable or an animal fiber even if an alkali orjan'acid or a usual neutral salt'ha's been added to the aqueous solution, which new compound when dyed with the addition of an alkali sulfid'has,

. paper and like purposes, this new compound l being most suitable for dyein leather and t more especially chrome leat ier from an acidulated bath, by which dyeing operation aqueous solution eliminates sulfurous acid deep black tints are obtained.

on the addition of a minerala'cid and which In testimony whereof I have hereunto set new compound in anaqueous solution on the i my hand in presence of two subscnbmg addition of an aqueous solution of a salt of l witnesses. copper, lead, barium, aluminum and like 1 EMIL HAUSSMANN. metals separates deeply colored lakes, which i lakes are suitable for example for coloring 1 compared with the original product, only a relatively very small affinity to the yegetable fiber and which new compound in an i Witnesses:

HENRY HASPER, WOLDEMAR HAUPT. 

